US8329966B2 - Slightly branched dialkyl benzenes and related compositions - Google Patents

Slightly branched dialkyl benzenes and related compositions Download PDF

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US8329966B2
US8329966B2 US11/907,273 US90727307A US8329966B2 US 8329966 B2 US8329966 B2 US 8329966B2 US 90727307 A US90727307 A US 90727307A US 8329966 B2 US8329966 B2 US 8329966B2
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base oil
olefins
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US20080103071A1 (en
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Chi-Hsing Tsai
Chien-Hsun Tsai
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Formosan Union Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C10M2203/065—Well-defined aromatic compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • This invention relates to synthetic base oil compositions comprising aromatic compounds with two long alkyl side chains—i.e., having carbon numbers from C 10 to C 28 —wherein the long alkyl side chains have precisely defined branching characteristics.
  • the synthetic base oil compositions of this invention have a combination of high viscometric index, low volatility, superior low temperature properties, and improved thermal/oxidation stability. They are particularly suitable for use as premium synthetic base stock, as a second base oil component, as diluents, or as additives for lubricant, fuel, and additive package applications.
  • High viscometric index, low volatilities, superior low temperature as well as thermal/oxidative stabilities are those of the most desirable and essential performance characteristics exhibited by synthetic lubricant base stocks such as polymerized alpha olefin base oils known/abbreviated as PAO.
  • PAO polymerized alpha olefin base oils
  • U.S. Pat. No. 6,869,917 teaches the use of PAO in the formulation of synthetic engine oil wherein PAO was claimed to exhibit viscometric index of, preferably, greater than 120, Selby-NOACK (abbreviated as NOACK) volatility from 4 to about 12%. A minimum NOACK volatility specification of 13% will be required for the future heavy diesel engine requirements.
  • NOACK Selby-NOACK
  • NOACK is the diesel lubricant specification proposed by Cummins in 2007, and cited as the minimum volatility for diesel engine oil other than 10W grades, by ACEA, EMA, and JAMA associations, Global Performance Specification for light duty diesel engine oil. Additionally, PAO was recognized as a wax free, synthetic composition with superior low temperature properties which are important for engine oil applications as it enhances engine oil pumpability/start up performance especially in cold climate conditions, and for a number of lubricant and additive applications that has no tolerance of crystallization/wax formation at low temperatures.
  • Refrigeration oil is an example that requires wax-free and outstanding low temperature properties, described in detailed in the Research Report sponsored by Air-Conditioning Research Institute, titled “Using Acid Number as indicator for refrigeration system performance”, ARTI-21CR/611-500, Final Report, 1993.
  • Substantially linear alkylphenols are proposed to ensure the wax free operations, see U.S. Pat. No. 5,600,025.
  • Waxy constitute in lubricants and additives can plug the in-line filtering devices in additive distribution systems and the fuel or lube systems of actual operating engines. Such a plugging would obviously be catastrophic and must be avoided.
  • Viscometric index higher than 120 is also the critical performance specification that separates GIII base oil, one of the highest categories of mineral oil based products, from that of lower grade GI and GII base oils. Because of this improvement and other performance benefits that are comparable to PAO with the exception in the region of low temperature properties, GIII base oil today is considered as “synthetic” base stock in Europe and North America.
  • esters in Synthetic Lubricants and High Performance Functional Fluids (2nd. ed.), Rudnick L R and Shubkin R L (eds.), Marcel Dekker, New York, pp. 63-101.
  • Esters have good additive solvency, however, is prone to hydrolysis and thermal/oxidative breakdown resulting in high acid/sludge formation tendency.
  • Oil soluble PAG or other polar base stocks offer some performance benefits, however, are often hygroscopic and problematic with compatibility with system components and the rest of the lubricant itself. Accordingly it is highly desirable to have a synthetic fluid that shall meet all of the above performance requirements and in the meantime to provide the additional performance features such as built-in solvency toward additives.
  • Synthetic heavy alkyl benzene fluids hereinafter referred as “heavy alkylates”, are commercially known as the by-products isolated from the detergent alkylate production by reacting olefins or paraffins feedstock with benzene. See the Handbook of Petroleum Refining Processes, McGraw-Hill, New York, Second Edition, 1977, by R. A. Meyers, pages 153-166.
  • heavy alkylates provide built-in solvency, excellent low temperature properties, and improved thermal/oxidative stability when compare with petroleum derived mineral oils, however, exhibit generally poor viscometric index and high volatility due to the fact that they contain a significant portion of isomerized/rearranged products other than the re-alkylated product of the detergent alkylate that include dialkylbenzene (abbreviated as DAB) as well as higher alkylates.
  • DAB dialkylbenzene
  • heavy alkylates based on branched olefins such as propylene tetramers gave poor VI less than 30 to even negative values
  • heavy alkylates based on linear olefins gave viscometric index generally between 40 and 110 that is not any better than those of the traditional mineral oil based products.
  • U.S. Pat. No. 3,173,965 discloses the high yield synthesis of DAB with a minimum of viscometric index of no less than 95 and a pour point of no more than 15° F. ( ⁇ 9.4° C.) through a two-step alkylation process in the presence of Friedel Crafts liquid acid catalysts such as HF, AlCl 3 , BF 3 , etc.
  • Suitable alkylating agents include pure linear alpha olefins or olefins made by wax or petrolatum cracking processes.
  • U.S. Pat. No. 4,148,834 further teaches the use of AlCl 3 or AlBr 3 in the above second step alkylation process wherein it improves the viscometric index of products that are made with HF catalyst.
  • U.S. Pat. No. 3,288,716 discloses the use of by-product alkylate bottom with a minimum viscosity index of at least 90, a ⁇ 40° C. viscosity of no higher than 25,000 cSt. and a pour point of at least—70° C., and a flash point of at least 430° F.
  • U.S. Pat. No. 6,491,809 teaches the production of DAB through the use of shape-selective solid catalysts by reacting benzene with linear alpha olefins.
  • the shape-selectivity of the catalysts minimizes the alkyl side chain isomerization and enables the exclusive formation of DAB with exceptionally high 2-linear isomer content.
  • the formation of high 2-linear isomer content gives the high viscometric index; however, it results in a DAB product with exceptionally high pour points, poor cold cranking viscosity, as well as high crystallization tendency at temperature as high as 0° C.
  • the present invention discloses the use of olefins with slight/controlled degree of branching, hereinafter called Slightly Branched Olefins, in the production of the DAB composition with a surprising and novel combination of performance benefits unmatched by the heavy alkylates as well as those described in the prior arts of the above.
  • This combination of performance benefits qualifies the DAB composition of the present invention as a stand-alone and premium synthetic base stock for a broad range of lubricant applications.
  • It's built-in benzene moiety provides the inherent solvency toward additives as well as additional performance benefits such as improved lubricity with and without additives, and hence it can also be used as ester replacements as a second base oil or additive component.
  • slightly branched DAB compositions which comprises primarily the di-alkylation products by reacting benzene in the presence of solid acid catalysts with Slightly Branched Olefins, wherein the olefins have carbon number ranged from C10 to C28, or C11-C24, or even more preferably C12-C18.
  • the branching characteristics of the slightly branched DAB are determined as follows:
  • the branching characteristics of the slightly branched DAB is defined by the “total methyl numbers (abbreviated as TMN)” determined by C 13 NMR spectroscopy to be from 2.1 to 3.5, preferably from 2.15 to 3.25, or even more preferably from 2.2 to 3.0.
  • TMN total methyl numbers
  • the Slightly Branched Olefins of the present invention are characterized by the “branching index (abbreviated as BI)” defined by the degree of the branching wherein BI is determined to be from more than 0.1 to less than 1.5, or more preferably, 0.15 to 1.25, or even more preferably, 0.2 to 1.0.
  • BI branching index
  • the Slightly Branched Olefins of the present invention can be either terminal, internal, or vinylidene type, or a mixture that contains at least one of such functionality types prepared under the isomerization/alkylation conditions with appropriate catalysts known in the art.
  • the slight branched olefins of the present invention can be selected from a single carbon range, such as C10, C11, C12, C13, C14, or C15 alike, or a mixture of different carbon ranges.
  • the Slightly Branched Olefins are obtained by the pre-isomerization of linear alpha olefins to olefins with desired branching characteristics, or through the dehydrogenation of paraffins followed by skeleton isomerization, or dehydrogenation of isoparaffins with desired branching characteristics generated by methods known in the arts, or alternatively, they can be generated in-situ via a simultaneous alkylation/isomerization process giving rise to appropriate branching characteristics desired by the present invention.
  • the Slightly Branched Olefins of the present invention can be prepared through olefin oligomerization such as hexene/octene dimerization or other chemistry such as Fischer Tropsch reactions known in the arts, to achieve desired branching, or through blending of olefins with different branching characteristics, for instance, by combing linear alpha olefins with branched olefins that can be selected from above.
  • the slightly branched DAB contains a mixture of poly-alkylated products that may be a di-, tri-, or higher alkylates, with DAB content greater than 85% and mono-alkylates content less than 0.5%.
  • the slightly branched DAB displays a novel and surprising combination of performance characteristics including a minimum viscometric index of 120, a maximum pour point of ⁇ 40° C., a Selby-NOACK (“NOACK”) volatility of no higher than 13%, and a cold cranking stimulated (“CCS”) viscosity at ⁇ 40° C. of no higher than 20,000 cp.
  • a minimum viscometric index of 120 a maximum pour point of ⁇ 40° C.
  • NOACK Selby-NOACK
  • CCS cold cranking stimulated
  • the DAB composition obtained in accordance with embodiments of the invention may be hydro-finished, clay treated, or processed to improve its color and appearance and can be used to formulate into lubricant oils in amounts from about 1% to 100%.
  • the lubricant oils may contain a number of additives and/or other base oils in amounts required to provide various functions desired by specific lubricant applications.
  • this invention provides a synthetic base oil composition
  • a synthetic base oil composition comprising a dialkyl aromatic compound with alkyl side chain carbon number from C10 to C28, wherein the branching characteristics of the said alkyl side chain has a total methyl number (TMN) determined by C 13 NMR spectroscopy to be from more than 2.1 to less than 3.5 or a branching index (BI) from more than 0.1 to less than 1.5.
  • TBN total methyl number
  • BI branching index
  • This synthetic base oil composition has a combination of high viscometric index, low volatility, superior low temperature properties, and improved thermal/oxidation stability that makes it suitable as a premium synthetic base stock, second base oil component, and additive for lubricant and additive package applications.
  • the synthetic base oil composition of this invention may be used in synthetic lubricant applications as base oil or additive component at a concentration from 1% to 99%.
  • FIG. 1A is a process flow chart illustrating formation of Slightly Branched Olefins via direct olefin isomerization.
  • FIG. 1B is a process flow chart illustrating formation of Slightly Branched Olefins via dehydrogenation of paraffins followed by olefin isomerization.
  • FIG. 1C is a process flow chart illustrating formation of Slightly Branched Olefins via dehydrogenation of isoparaffins with desired branching.
  • FIG. 1D is a process flow chart illustrating formation of Slightly Branched Olefins via in situ formation of isomerized/Slightly Branched Olefin followed by in situ alkylation with benzene.
  • FIG. 2 illustrates the relationship between the total methyl carbon numbers (abbreviated as TMN) and branching index (abbreviated as BI).
  • FIG. 3 plots TMN value versus viscometric index of the examples of the present invention, wherein the maximum of TMN values are extrapolated up to 3.5 in order to achieve the minimum viscosity index of 120.
  • This invention provides a synthetic base oil composition
  • a dialkyl aromatic compound having an alkyl side chain carbon number from C 10 to C 28 , preferably from C 11 to C 24 , more preferably from C 12 to C 18 .
  • the branching characteristics of the dialkyl side chains has a total methyl number (“TMN”) determined by C 13 NMR spectroscopy of from more than 2.1 to less than 3.5 or has a branching index (“BI”) of from more than 0.1 to less than 1.5.
  • the TMN of said dialkyl aromatic compound is from 2.15 to 3.25 or wherein the BI is from 0.15 to 1.25.
  • the TMN of said dialkyl aromatic compound is from 2.2 to 3.0 or wherein the BI is from 0.2 to 1.0.
  • the content of dialkyl aromatic compound is at least 85% by weight, based on the total weight of the synthetic base oil composition.
  • the aromatic compound is a member selected from the group consisting of benzene, toluene, biphenyl oxide, biphenyl, anisole, naphthalene, and methylnaphthalene.
  • the synthetic base oil composition of this invention typically has a minimum viscometric index of 120, a maximum pour point of ⁇ 40° C., a Selby-NOACK (“NOACK”) volatility of no higher than 13%, and a cold cranking stimulated (“CCS”) viscosity at ⁇ 40° C. of no higher than 20,000 cp.
  • NOACK Selby-NOACK
  • CCS cold cranking stimulated
  • the synthetic base oil composition of this invention may further comprises additional synthetic alkylates which are linear or branch types.
  • the present synthetic base oil composition can further comprise a second synthetic base oil selected from the group consisting of polymerized alpha olefin base oil and mineral oil.
  • the present synthetic base oil may further comprise a lubricant additive.
  • Another embodiment of the invention is a method of making the synthetic base oil composition described herein.
  • This method comprises alkylating an aromatic compound with an olefin that is linear, terminal, internal, vinylidene, or branch type, or a mixture thereof, and isomerizing the resulting alkylated aromatic compound to provide the specified branching characteristics in said alkyl side chains.
  • These alkylating step and isomerizing steps may be carried out in the presence of solid acid catalyst selected from the group consisting of clay, amorphous silica-alumina, and zeolite in a recycle mode or two steps mode to produce said dialkyl aromatic compound in major amounts.
  • the alkylating step and isomerizing steps are carried out in a recycle mode or in a two steps mode to produce the desired dialkyl aromatic compound in major amounts.
  • the olefin is prepared by the steps of: a) isomerizing a paraffin to produce an isoparaffin, b) dehydrogenating the resulting isoparaffin-containing stream to produce a mono-olefin-containing stream, and c) selectively hydrogenating the mono-olefin stream to remove dienes and to produce mono-olefins having the specified branching characteristics required for said alkyl side chains.
  • the olefin is prepared by the step of: conducting a shape-selective olefin oligomerization and/or isomerization process to produce mono-olefins having the specified branching characteristics required for said alkyl side chains. Additional variations of this method include preparing the olefin by the step of: conducting a Fischer-Tropsch process to produce mono-olefins having the specified branching characteristics required for said alkyl side chains, and preparing the olefin by the step of: blending and/or mixing linear and branch olefins to produce mono-olefins having the specified branching characteristics required for said alkyl side chains.
  • the aromatic feedstock comprises an aromatic moiety, which is preferably benzene, or alternatively, any aromatic compound including toluene, ethylbenzene, xylene, anisole, naphthalene, methylnaphthalene, or derivates of the above that may be alkylated with Slightly Branched Olefins.
  • aromatic compound other than benzene must be exercised with care as it may limit/alter the degree of alkylation that ultimately will impact the performance characteristics of the DAB base stock composition
  • the Slightly Branched Olefins of the present invention can be either terminal, internal, or vinylidene type, or a mixture that contains at least one of such functionality types prepared under the isomerization/alkylation conditions with appropriate catalysts known in the art.
  • FIG. 2 describes the relationship between the total methyl carbon numbers (abbreviated as TMN) and branching index (abbreviated as BI).
  • TMN is the total carbon numbers that belong to the structural type of methyl groups on the alkyl side chains of the DAB composition of the present invention.
  • the characterization, assignment, and quantitative determination of methyl groups have been carried out routinely with analytical techniques such as Infrared spectroscopy as disclosed in U.S. Pat. No. 5,922,922 NMR (H 1 and C 13 ) spectroscopy, or other methods known in the arts.
  • the Slightly Branched Olefin may comprise a mixture of linear and branched molecules that can be mono-substituted, di-substituted, or tri-substituted wherein its branching characteristics is defined by either TMN or BI values as shown in FIG. 2 and calculated/determined by C 13 NMR spectroscopic method in accordance with the following equations:
  • the alkyl group branch or branches of the Slightly Branched Olefins can be bonded to any carbon on the aliphatic olefin chain in the molecules and may be selected from methyl, ethyl, propyl, or alike, or a mixture of all of the above.
  • the olefin functionalities of the Slightly Branched Olefins of the present invention can be either terminal (or called alpha), vinylidene, or internal type, or a mixture that contains at least one of such functionality types as described in the general formula of the following: R 1 R 2 —C ⁇ C—R 3 R 4
  • terminal/alpha olefins refers to olefins having the chemical formula of R 1 —CH ⁇ CH 2 (R 2 , R 3 , R 4 ⁇ H).
  • vinylidene refers to olefins having the chemical formula of R 1 R 2 —C ⁇ CH 2 (R 3 , R 4 ⁇ H).
  • internal olefins refers to olefins having the chemical formula of R 1 R 2 —C ⁇ CR 3 R 4 (at least one aliphatic, non-hydrogen groups attached to the olefin functionality).
  • the total carbon number of the DAB composition must exceed C26, or more preferably C28, at a concentration more than 90%. By doing so, NOACK volatility is expected to be 13% or less.
  • Another consideration in the selection of chain length of the DAB composition is viscosity. Generally the higher the alkyl chain length, the higher the viscosity grade of DAB composition may be achieved.
  • Slightly Branched Olefins is not the essential element of the present invention, and without being bonded by any theory, they can be produced by either paraffins dehydrogenation or paraffin/olefin isomerization through shape-selective solid catalysts such as ZSM-5 and ZSM-23 as disclosed in U.S. Pat. No. 4,855,527, or a combination of processes described in Parts 1 and 2 in FIG. 1 and/or any other processes known in the arts to achieve the desire branching characteristics.
  • Such slight branched olefins may also be produced in situ during the alkylation process wherein the olefins may be isomerized and subsequently/simultaneously alkylated in the presence of solid acid alkylation catalysts as described in FIG. 1.
  • the alkylation process employed to prepare the DAB composition of the present invention may be carried out with a number of alkylation solid catalysts known/skilled in the arts. Examples include clay, amorphous silica-alumina, zeolite, or alike, but shall not be limited to the above.
  • the DAB composition so prepared matches and exceeds critical performance characteristics including high viscometric index, low volatility, superior low temperature properties, and improved thermal/oxidation stability unmatched by the heavy alkylate as well as those disclosed in the prior arts of the above.
  • This combination of performance benefits enable its use as a premium synthetic lubricant base stock wherein it can be used as a standalone base stock, a second base oil component, or additive whenever is appropriate.
  • the DAB composition of the present invention may be further processed through hydro-finishing, clay treated, or processes known in the arts to improve its color and appearance characteristics and to remove residual impurities such as moisture or residual catalyst present.
  • Such additional processing is known in the arts to produce fluids that are more suitable for high sensitive and critical applications such as insulating/cable fluids and refrigeration oils where it requires superior electrical properties.
  • the performance characteristics of the DAB composition of the present invention can be further improved and expanded by the addition of additive such as antioxidants and other additives known in the trade of lubricant formulations, to meet requirements of specific functions of the intended applications.
  • alkylation catalyst such as mordenite-type zeolite was used to demonstrate the merits and importance of employing Slightly Branched Olefins for making the DAB composition of the present invention that contain primarily DAB alkylates.
  • Table 1 assigns fluid ID to each of the examples and comparative examples with key/summary information. It should be understood that discussions provided hereinafter are served for the purpose of illustration and are not meant to limit the scope of this invention to the embodiments shown in the examples.
  • the C 12 -based DAB products are separated from the resulting product mixture by distillation to remove mono-alkylbenzene to less than 0.5%.
  • the C 12 -based DAB products are characterized by NMR and other analytical methods.
  • Example 1 Benzene and dodecene sourced from Innovene with C12 alpha olefin purity of 85% and C12 branched and vinylidene olefins of 11% were reacted according to the same procedure/process conditions given in Example 1 with an inlet temperature of 190° C.
  • the C12-based DAB products are isolated and characterized as described in Example 1
  • Tetra-decenes sourced from Mitsubishi Chemical was isomerized with zeolite catalyst to give the isomerized C14 olefins with alpha olefin purity of 4% and branched and vinylidene olefins of more than 75%. Benzene and pre-isomerized olefins are then reacted according to the same procedure/process conditions given in Example 1 with an inlet temperature of 200° C. The C14-based DAB products are isolated and characterized as described in Example 1
  • Example 1 Benzene and tetra-decenes sourced from Innovene with alpha olefin purity of 74% and C14 branched and vinylidene olefins of 18% were reacted according to the same procedure/process conditions given in Example 1 with an inlet temperature of 220° C.
  • the C14-based DAB products are isolated and characterized as described in Example 1
  • Benzene and branched olefins namely butene trimers and propylene tetramers respectively were allowed to react in the commercial process using HF catalysts.
  • the heavy products was isolated after the removal of mono-alkylates as well as intermediate products between DAB and mono-alkylates and characterized as described in Example 1.
  • Comparative examples of 8-11 are commercial samples selected for comparison.
  • the composition/catalyst is listed in Table 1.
  • Tables 2, 3 summarize process conditions, branching characteristics of olefins/alkyl side chain, viscometric properties, and performance data on examples provided above.
  • Comparative Examples 1-3 Fluds C/D/E, see Table 1&2), that the use of mordenite and commercially available C12 linear alpha olefins (pure alpha olefin used in Comparative Example 3) gives DAB with high 2-linear isomer content and thereby high viscometric index but fails consistently to give good low temperature properties as measured by cold cranking simulated/CCS viscosity at ⁇ 40° C.
  • CCS is the critical test required to exemplify the pumpability and start up ability of the lubricant at low temperatures.
  • Fluid I is an example wherein a mixture of linear olefin was used in the preparation of DAB.
  • Such an approach which is commonly employed in the arts to tailor/optimize base oil properties, gives some improvements on pour points, however, fails to give measurable CCS viscosity at ⁇ 40° C.
  • Fluid J and K based on BT (BI of approximately 2) and PT (BI of approximately 3) olefins respectively using HF catalyst are provided for comparative purpose.
  • the alkylate products isolated after the removal of mono-alkylates and light ends were found to contain DAB as well as tri-alkylated products. Results given in Table 4 showed that they have low/unacceptable volatility and far inferior viscometric index characteristics than DAB prepared by the present invention.
  • TMN and BI branching relationship between TMN and BI given in FIG. 2 can be further illustrated in the Table 5 below that include present examples as well those known in the arts.
  • Higher carbon numbers of alkyl side chain of said dialkyl benzene is expected to give higher viscometric index.
  • C14 based DAB of the present invention at a higher TMN (2.5-2.6) gives VI comparable with C12 based DAB with lower TMN (2.1-2.4).
  • Higher TMN is anticipated with higher alkyl side chains.

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US20160319214A1 (en) * 2013-12-20 2016-11-03 Whirlpool S.A. Oil, Lubricant Composition Having Improved Lubricity and Increased Coefficient of Performance, Uses and Mechanical Equipment

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US9074143B2 (en) * 2009-12-11 2015-07-07 Uop Llc Process for producing hydrocarbon fuel
US8193401B2 (en) * 2009-12-11 2012-06-05 Uop Llc Composition of hydrocarbon fuel
US9238599B2 (en) 2011-12-07 2016-01-19 Exxonmobil Chemical Patents Inc. Alkylaromatic process
US20140274838A1 (en) * 2013-03-15 2014-09-18 Exxonmobil Research And Engineering Company Method for improving thermal-oxidative stability and elastomer compatibility
US9822046B1 (en) * 2016-05-19 2017-11-21 Chevron U.S.A. Inc. Farnesane alkylation
US10093594B2 (en) 2016-05-19 2018-10-09 Chevron U.S.A. Inc. High viscosity index lubricants by isoalkane alkylation

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US20160319214A1 (en) * 2013-12-20 2016-11-03 Whirlpool S.A. Oil, Lubricant Composition Having Improved Lubricity and Increased Coefficient of Performance, Uses and Mechanical Equipment

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EP1916289B8 (fr) 2012-02-08
EP1916289A1 (fr) 2008-04-30
US20080103071A1 (en) 2008-05-01
ATE509083T1 (de) 2011-05-15
ES2366582T3 (es) 2011-10-21
JP2008106274A (ja) 2008-05-08
EP1916289B1 (fr) 2011-05-11

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